phosphoric acid diethyl ester 1-methyl-3-oxo-but-1-enyl ester | 5675-58-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: phosphoric acid diethyl ester 1-methyl-3-oxo-but-1-enyl ester
• 英文别名: Phosphorsaeure-diaethylester-(1-methyl-3-oxo-but-1-enylester)；4-Diaethoxyphosphoryloxy-pent-3-en-2-on；diethyl 4-oxopent-2-en-2-yl phosphate
• CAS: 5675-58-1
• 化学式: C₉H₁₇O₅P
• 分子量: 236.205
• InChiKey: AHOFSKMNZFFOAD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.68
• 重原子数：
  15.0
• 可旋转键数：
  7.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  61.83
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  phosphoric acid diethyl ester 1-methyl-3-oxo-but-1-enyl ester 在 lithium aluminium deuteride 作用下， 以 乙醚 、 氯仿 为溶剂， 反应 4.0h， 生成
  参考文献：
  名称：

  Stereochemistry in the Ene Reactions of Singlet Oxygen and Triazolinediones with Allylic Alcohols. A Mechanistic Comparison

  摘要：

  The ene reaction of singlet oxygen with (Z)-4-methylpent-3-en-2-ol-2,5,5,5-d(4) (1-OH-d4) in nonpolar solvents exhibits a 90% three diastereoselectivity in the adduct derived from the major syn perepoxide intermediate, but also a moderate three diastereoselectivity in the adduct derived from the minor anti perepoxide. Photooxygenation of 2,4-dimethylpent-3-en-2-ol (2) exhibits a significant solvent dependence in the syn/anti methyl stereoselectivity, with nonpolar solvents promoting syn methyl reactivity, while polar solvents promote anti methyl reactivity. These results are in agreement with a steering effect between hydroxyl and singlet oxygen in the rate-determining step of the reaction. N-Phenyltriazolinedione addition to the chiral allylic alcohol 4-methylpent-3-en-2-ol (1-OH) is highly three diastereoselective in nonpolar solvents, with a solvent dependent variation in the threo/erythro ene products. On the other hand, the nonfunctionalized chiral alkene 2,4-dimethyl-2-hexene (1-Et) exhibits poor diastereoselectivity. Reaction of PTAD with 1-OH-d4 in nonpolar solvents, exhibits a significant three diastereoselectivity from the syn aziridinium imide intermediate, and a moderate three diastereoselectivity from the anti intermediate. These results are consonant with a steering effect between the hydroxyl and the electrophile, as proposed in the case of singlet oxygen addition to allylic alcohols 1-OH and 2. In contrast to the analogous O-1(2) ene reaction, a solvent independent ratio syn/anti similar to 50/50 was found in the addition of MTAD to 2. The intermolecular kinetic isotope effect in the reaction of 2 with MTAD (k(H)/k(D) = 1.15 +/- 0.02), is consistent with formation of the intermediate in fast step, indicative that the steering effect during the formation of aziridium imide is not important in the reaction kinetics. This energetic profile is in contrast to triazolinedione addition to the secondary allylic alcohol 1-OH, where the high three selectivity and the slight inverse kinetic isotope effect of k(H)/k(D) = 0.98 +/- 0.02 are consonant with the formation of the intermediate in the rate-determining step. An explanation for the increased reactivity of the syn methyl in the addition of MTAD to 2 (similar to 50%) is offered.

  DOI：

  10.1021/jo990258b
• 作为产物：
  描述：

  氯磷酸二乙酯 、 乙酰丙酮 在 sodium hydride 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以89%的产率得到phosphoric acid diethyl ester 1-methyl-3-oxo-but-1-enyl ester
  参考文献：
  名称：

  Stereochemistry in the Ene Reactions of Singlet Oxygen and Triazolinediones with Allylic Alcohols. A Mechanistic Comparison

  摘要：

  The ene reaction of singlet oxygen with (Z)-4-methylpent-3-en-2-ol-2,5,5,5-d(4) (1-OH-d4) in nonpolar solvents exhibits a 90% three diastereoselectivity in the adduct derived from the major syn perepoxide intermediate, but also a moderate three diastereoselectivity in the adduct derived from the minor anti perepoxide. Photooxygenation of 2,4-dimethylpent-3-en-2-ol (2) exhibits a significant solvent dependence in the syn/anti methyl stereoselectivity, with nonpolar solvents promoting syn methyl reactivity, while polar solvents promote anti methyl reactivity. These results are in agreement with a steering effect between hydroxyl and singlet oxygen in the rate-determining step of the reaction. N-Phenyltriazolinedione addition to the chiral allylic alcohol 4-methylpent-3-en-2-ol (1-OH) is highly three diastereoselective in nonpolar solvents, with a solvent dependent variation in the threo/erythro ene products. On the other hand, the nonfunctionalized chiral alkene 2,4-dimethyl-2-hexene (1-Et) exhibits poor diastereoselectivity. Reaction of PTAD with 1-OH-d4 in nonpolar solvents, exhibits a significant three diastereoselectivity from the syn aziridinium imide intermediate, and a moderate three diastereoselectivity from the anti intermediate. These results are consonant with a steering effect between the hydroxyl and the electrophile, as proposed in the case of singlet oxygen addition to allylic alcohols 1-OH and 2. In contrast to the analogous O-1(2) ene reaction, a solvent independent ratio syn/anti similar to 50/50 was found in the addition of MTAD to 2. The intermolecular kinetic isotope effect in the reaction of 2 with MTAD (k(H)/k(D) = 1.15 +/- 0.02), is consistent with formation of the intermediate in fast step, indicative that the steering effect during the formation of aziridium imide is not important in the reaction kinetics. This energetic profile is in contrast to triazolinedione addition to the secondary allylic alcohol 1-OH, where the high three selectivity and the slight inverse kinetic isotope effect of k(H)/k(D) = 0.98 +/- 0.02 are consonant with the formation of the intermediate in the rate-determining step. An explanation for the increased reactivity of the syn methyl in the addition of MTAD to 2 (similar to 50%) is offered.

  DOI：

  10.1021/jo990258b

文献信息

• A general method of synthesis of functionalized Z-vinylic tellurides starting from β-dicarbonyl compounds
  作者：Rafael E Barrientos-Astigarraga、Priscila Castelani、Celso Y Sumida、Julio Zukerman-Schpector、João V Comasseto

  DOI：10.1016/s0040-4020(01)01204-2

  日期：2002.2

  Z-Vinylic tellurides are prepared by stereoselective vinylic substitution on Z/E mixtures of enolphosphates, acetates, tosylates and triflates by organotellurolates. The reaction is sensitive to the nature of the organotellurolate; the aromatic derivatives react slower than the aliphatic ones. The reaction time is not influenced by the nature of the leaving group.

  Z- Vinylic碲化物是通过在烯醇磷酸酯，乙酸酯，甲苯磺酸酯和三氟甲磺酸酯的Z / E混合物上通过立体立体乙烯基化合物进行立体选择性乙烯基取代而制得的。该反应对有机碲酸根的性质敏感。芳香族衍生物的反应比脂肪族衍生物慢。反应时间不受离去基团性质的影响。
• Synthesis of functionalized tri- and tetrasubstituted vinylic tellurides from enolphosphates through vinylic substitution by lithium butyltellurolate
  作者：R.E Barrientos-Astigarraga、P Castelani、C.Y Sumida、J.V Comasseto

  DOI：10.1016/s0040-4039(99)01633-0

  日期：1999.10

  Vinylic tellurides are precursors of important highly reactive vinylic organometallics (e.g. vinyl Li and Cu species). Herein we report that tri- and tetrasubstituted functionalized vinylic tellurides can be prepared from enolphosphates through a vinylic substitution by lithium butyltellurolate. Starting from mixtures of Z- and E-enolphosphates, only the Z-vinylic telluride is formed.

  乙烯基碲化物是重要的高反应性乙烯基有机金属（例如乙烯基Li和Cu物质）的前体。在本文中，我们报道可以通过烯丙基磷酸酯通过碲酸丁二酸锂的乙烯基取代来制备三和四取代的官能化的乙烯基碲化物。从Z-和E-烯醇磷酸酯的混合物开始，仅形成Z-乙烯基碲化物。
• Diastereoselective synthesis of α,β-unsaturated systems
  作者：Priscila Castelani、João V. Comasseto

  DOI：10.1016/j.tet.2005.01.025

  日期：2005.2

  Functionalized Z-vinylic tellurides were used in substitution reactions with lower order cyanocuprates leading to alpha, beta-unsaturated ketones and esters in good yields. In the case of acyclic tellurides, the product was obtained in high diastereoselectivity. The control of the stereoselectivity was achieved by simple change of the reaction temperature. (C) 2005 Elsevier Ltd. All rights reserved.
• Über die Darstellung von Enol-phosphaten und Enol-phosphinaten aus Carbonylverbindungen
  作者：N. Kreutzkamp、J. Pluhatsch、H. Schindler

  DOI：10.1002/ardp.19602931005

  日期：——
• Kabachnik,M.I. et al., Journal of general chemistry of the USSR, 1960, vol. 30, p. 2201 - 2205
  作者：Kabachnik,M.I. et al.

  DOI：——

  日期：——